Solid,curable compositions containing oxoalkyl acrylamides

ABSTRACT

SOLID, CURABLE SOLUTIONS OR DISPERSIONS ARE FORMED BY BLENDING A POLYMER SUBSTANTIALLY FREE OF ETHYLENIC UNSATURATION, USUALLY A THERMOPLASTIC POLYMER, WITH AN OXOALKYL-SUBSTITUTED ACRYLAMIDE SUCH AS DIACETONE ACRYLAMIDE, HEATING TO ABOVE THE MELTING POINT OF THE LATTER, AND THEN COOLING. THEY MAY BE CURED (E.G., BY THE ACTION OF A FREE RADICAL CATALYST) UNDER RELATIVELY UNSOPHISTICATED CONDITIONS, SUCH AS IN THE HOME, TO FORM USEFUL AND DECORATIVE COATINGS, LAMINATES AND ADHESIVES.

United States Patent 3,816,559 SOLID, CURABLE COMPOSITIONS CONTAININGOXOALKYL ACRYLAMIDES Eugene Richard Farone, Mentor-on-the-Lake, Ohio,as-

signor to The Lubrizol Corporation, Wickliife, Ohio No Drawing.Continuation of abandoned application Ser.

No. 56,698, July 20, 1970. This application Mar. 2,

1972, Ser. No. 231,401

Int. Cl. C08g 41/04 US. Cl. 260-857 8 Claims ABSTRACT OF THE DISCLOSUREThis is a continuation of application Ser. No. 56,698, filed July 20,1970, now abandoned.

This invention relates to new compositions of matter capable of beingcured into useful resinous products. More particularly, it relates tocompositions which are solid at room temperature, said compositionscomprising (A) a polymer substantially free of ethylenic unsaturationand (B) a compound of the formula 0 R R 0 m l s 'l c=em R R H in whereineach of R R and R is hydrogen, a hydrocarbon radical, or a hydroxyalkylor alkoxyalkyl radical,

each of R and R is hydrogen or a hydrocarbon radical, and R is hydrogen,halogen or a lower alkyl radical;

said compositions being capable of forming, at elevated temperatures, asolution or dispersion.

The present invention finds application in the preparation of laminates,coatings, adhesive films and the like under relatively unsophisticatedconditions such as those found in the home. Solutions and dispersions ofresins in volatile solvents are, of course, well known in the art.However, such solutions and dispersions are unsuitable for use for manypurposes in the home because of the difiiculties and dangers involved inremoving the solvent. It is of advantage, therefore, to preparepolymeric compositions which are entirely or substantially non-volatileand which can be converted to resinous products using ordinary homeappliances.

A principal object of the invention, therefore, is to provide newpolymeric compositions which are entirely or substantially non-volatileat room temperature.

A further object is to provide compositions which are partly polymericand partly monomeric in nature, and which can be cured under relativleysimple conditions to form laminates, coatings and the like.

Still another object is to provide useful resinous compositions.

Other obiects will in part be obvious and will in part appearhereinafter.

Component A in the compositions of this invention is a polymersubstantially free of ethylenic unsaturation. This polymer may bethermoplastic, and thermoplastic ones are preferred; or it may bethermosetting or thermoset, the word thermosetting denoting a polymerwhich is capable of crosslinking or curing to form an infusible product,and the word thermoset denoting a polymer which has already been socrosslinked or cured.

The polymers should be substantially free of ethylenic unsaturation soas to avoid a substantial amount of crosslinking with component B. Ingeneral, component A should contain not more than about one ethylenicunit for each 20 polymeric units in the chain.

The following are illustrative of resins which may be used as componentA.

I. Thermoplastic resins: Polymers of vinyl halides such as vinylchloride and vinyl bromide; of polymerizable esters such as vinylacetate, vinyl propionate, methyl acrylate, methyl methacrylate, ethylacrylate, n-butyl acrylate, trimethylolpropane trimethacrylate and thelike; of unsaturated hydrocarbons such as ethylene (especiallylowdensity polyethylene), propylene, the butenes, styrene and the like;copolymers and interpolymers of vinyl halides with polymerizable esters,especially vinyl acetate; saturated polyamides and polyesters.

II. Thermosetting resins: Uncured epoxy resins, lightly crosslinkedpolymers of alkyl acrylates, A-stage phenolic resins.

III. Thermoset resins: B-stage phenolic resins, cured epoxy resins.

Component B in the compositions of this invention is,

as previously indicated, a compound of the formula wherein each of R isas defined. As used in the formula and elsewhere herein, the termhydrocarbon radical includes aliphatic, cycloaliphatic and aromatic(including aliphatic-substituted aromatic and aromatic-substitutedaliphatic) radicals. Substituted hydrocarbon, alkyl, aryl, etc.,radicals are considered to be fully equivalent to the hydrocarbon,alkyl, aryl, etc., radicals and to be part of this invention. Bysubstituted is particularly meant radicals containing relatively inertsubstituents such as other (especially lower alkoxy), ester (especiallylower carbalkoxy), keto, nitro, halogen and the like so long as thesesubstituents do not alter significantly the character or reactivity ofthe radical. In general, no more than about three such substituentgroups will be present for each 10 carbon atoms in the radical.

The following are illustrative of hydrocarbon and substitutedhydrocarbon radicals within the scope of this invention.

CHa

-crnom -CH2CHzCHs --CHCH:

--(CH2)uCHCHiCHa CH: CH:

- --CH2 CH:

Ha Ha CH=CH:

Preferably, the hydrocarbon or substituted hydrocarbon radicals in thecompounds used in the composition of this invention are lowerhydrocarbon radicals, the word lower denoting radicals containing nomore than about 12 carbon atoms. Still more preferably, they are loweralkyl or aryl radicals, most often alkyl. In the most preferredcompounds, R is lower alkyl (usually) or a radical of the formula R' OR-CH wherein R is hydrogen or lower alkyl and R is a divalent hydrocarbonatom having less than five carbon atoms, usually methylene; each of Rand R is hydrogen (usually) or R OR R and R are lower alkyl; and R ishydrogen or methyl. Especially useful are compounds in which R R and Rare lower alkyl and R R and R are hydrogen.

The following are illustrative of the compounds which may be used ascomponent B in the compositions of this invention.

N-(1,1-dlmethyl-3-oxobutyl) acrylamide (diacetone acrylamide) O CH:CHa-CHaC-NHC O CH= CH:

N- (1,3-diphenyl-1-methyl-3-oxopropyl) methacrylamide O CH: CcHs-CHz-NHCO C CH:

CIHI

N- (1,1-dlmethy1-3-0xobutyl -2-chloroacrylamide O CH; CH: -CH;CNHC 0 CCH:

CH: Cl N- (1,1-diethy1-5-hydroxy-3-oxopentyl) methacrylamide O C 1115 HOCHzCH:( .CHaC-NHC 0 C CH:

01H CH:

N- [1,1-dimethyl-2,2-bis (hydroxymethyl) -5-hydroxy-3-oxopeutyl1-acrylamlde 0 CHzOH CHa HOCH2CHzC--C NHC O CH=CH1 CHQOH CH;N-[1,1-dlmethyl-2,2-bis(nbutoxymethyl)-5-n-butoxy-3-oxopeutyl1acrylamide O CHaO ClHn CH:

The preparation of compounds of this type wherein R are hydrogen orhydrocarbon radicals and R is hydrogen or lower alkyl is described inUS. Pats. 3,277,- 056 and 3,425,942, the disclosures of which areincorporated by reference herein. Similar compounds wherein one or moreof R are hydroxyalkyl or alkoxyalkyl radicals are disclosed in copendingapplications Ser. No. 833,162, filed June 13, 1969, and Ser. No.111,676, filed Feb. 1, 1971. Compounds in which R is a halogen atom,while they may be used in the compositions of this invention, are notthemselves part of the invention. They are disclosed and claimed incopending application Ser. No. 97,055, filed Dec. 10, 1970, now US. Pat.3,666,306.

The compounds most particularly useful as component B are diacetoneacrylamide and diacetone methacrylamide, especially the former. For thesake of convenience and brevity herein, frequent reference will be madehereinafter to diacetone acrylamide as representative of the genus;however, it is to be understood that other compounds of the genus may besubstituted for diacetone acrylamide.

The proportions of the ingredients in the compositions of this inventionare generally within the range of 2-70 parts (by weight) of component Aand 98-3O parts of component B, respectively. Most often, component A isthe solute or discontinuous phase and is therefore present in minoramounts as compared with component B; that is, less than 50 parts ofcomponent A per 100 parts of the combination of components A and B. Thecompositions may also contain minor amounts (e.g., up to about 2.5 partseach per 100 parts of the combination of components A and B) of otheringredients, especially antioxidants such as hindered phenols andpolymerization catalysts, usually free radical catalysts such as benzoylperoxide, t-butyl hydroperoxide, acetyl peroxide, azobisisobutyronitrileand the like.

Volatile solvents may also be present in small amounts to aid inmaintaining proper viscosity, solubility or dispersibility of componentsA. Typical voltaile solvents which may be used include aromatichydrocarbons such as benzene, toluene and xylene; chlorinated aliphatichydrocarbons such as 1,2-dichloroethane, 1,1,1-trichloroethane and thelike; alcohols such as methanol, ethanol, 1- propanol, 2-propanol or oneof the butanols; lower alkyl monoand diethers of glycols such asethylene glycol or diethylene glycol; ketones such as acetone, methylethyl ketone or methyl isobutyl ketone; and relatively low molecularweight esters such as ethyl acetate, butyl acetate, ethyl propionate andthe like.

The compositions of this invention are prepared by merely blending thecomponents and heating to above the melting point of diacetoneacrylamide, thereby liquefying the latter and causing the formation of asolution or dispersion of the polymer therein. Generally, temperaturesof about 60100 C. are adequate. Especially if the composition alsocontains a polymerization catalyst, as is usually the case, temperaturesmuch above 100 C. should be avoided since component B will polymerize ifthe temperature is too high. Upon cooling, the compositions resolidify.

When liquid, the compositions of this invention may be solutions ordispersions depending upon the solubility of component A in component B.In general, this solubility increases with increasing polarity of thepolymer used as component A. Thus, polar polymers such as polyacrylates,polyvinyl acetate, polyvinylbutyral and the like form solutions, whileless polar polymers such as polyvinyl chloride, polyethylene andpolypropylene form dispersions. Both types of compositions are includedin the present invention. It is also within the scope of this inventionto use a mixture of polymers as component A, or to add to thecomposition curable polymers such as unsaturated polyesters, orcrosslinking agents such as styrene, diallyl phthalate or the like.

The following examples are illustrative of the compositions of thisinvention. All parts are by weight.

EXAMPLE 1 Parts Polyamide resin (Versamid 950) 20 Trimethylolpropanetrimethacrylate 10 Diacetone acrylamide 200 2,6Di-t-butyl-p-cresol 0.2

The above components are blended and the blend is heated to 65-70" C.,whereupon a dispersion forms.

EXAMPLE 2 Parts Copolymer of lower alkyl acrylates and methacrylates(Acryloid B-82) Trimethylolpropane trimethacrylate 10 Diacetoneacrylamide 200 2,5-Dimethylhexane-2,S-diperoctoate 2 2,6-Di-t-butyl-pcresol 0.2

Upon blending these components and heating to 70- 75 C., the mixturefuses and forms a solution.

EXAMPLE 3 Parts Copolymer of lower alkyl methacrylates, mostly methylmethacrylate (Acryloid B-66) 20 Trimethylolpropane trimethacrylate 10Diacetone acrylamide 200 2,5-Dimethy1hexane-2,S-diperoctoate 22,6-Di-t-butyl-p-cresol 0.2

Upon blending and heating to 70-75" C., a solution forms as in Example2.

EXAMPLE 4 Parts Trimethylolpropane trimethacrylate l Diacetoneacrylamide 200 2,5-DimethylheXane-2,S-diperoctoate 22,6-Di-t-butyl-p-cresol 0.2

The mixture is heated to 70 C., whereupon a solution forms.

EXAMPLE 5 Parts Trimethylolpropane trimethacrylate Methylolated monomerobtained by reacting one mole of diacetone acrylamide with one mole offormaldehyde, under alkaline conditions 2002,5-Dimethylhexane-2,5-diperoctoate 2 2,6-Di-t-butyl-p-cresol Uponheating, a solution similar to that of Example 4 6 EXAMPLE 7 PartsTerpolymer containing about 86% vinyl chloride units, about 13% vinylacetate units, and about 1% maleic anhydride units 10 Diacetoneacrylamide 50 Upon heating as in Example 6, a solution forms.

EXAMPLE 8 Parts Polyvinyl chloride powder (Geon 101) 20 Diacetoneacrylamide 50 Upon heating to about 70 C., a dispersion forms.

EXAMPLE 9 Parts Polyvinyl chloride powder of Example 8 20 Methylolatedmonomer of Example 5 50 A dispersion similar to that of Example 8 forms.

EXAMPLE 10 Parts Polyvinyl chloride powder of Example 8 30 Diacetoneacrylamide 50 Upon heating to 70 C., a dispersion similar to that ofExample 8 forms.

EXAMPLE 11 Parts Polyvinyl chloride powder of Example 8 60Trimethylolpropane trimethacrylate 10 Diacetone acrylamide 100 t-Butylperbenzoate 2 2,6-Di-t-butyl-p-cresol 0.1

Upon heating to 70 C. a viscous dispersion forms.

EXAMPLE 12 Parts Low-density polyethylene 33 Diacetone acrylamide 100t-Butyl perbenzoate 1 Upon heating to about 70 C., a fluid dispersionforms.

EXAMPLE 13 Parts Polyvinyl butyral 100 Diacetone acrylamide 3002,6-Di-t-butyl-p-cresol 0.1

Upon heating to -85 C., a viscous dispersion forms.

EXAMPLE 14 Parts Polyvinyl butyral Methylolated monomer of Example 5 3002,6-Di-t-butyl-p-cresol 0.1

Upon heating to 80-85 C., a dispersion similar to that of Example 13forms.

EXAMPLE 15 Parts Polyvinyl acetate 300 Diacetone acrylamide 3002,6-Di-t-butyl-p-cresol 0.1

Upon heating to 80-85 C. with stirring, a viscous dispersion forms.

The compositions of this invention may be liquefied and component Btherein polymerized under relatively simple conditions to form usefulcoatings, films, adhesives and the like. Compositions that alreadycontain a free radical catalyst (cf. Examples 2-5, 11, 12, 14 and 15)may be polymerized merely by heating. Compositions not containing such acatalyst (cf. Examples 1, 6-10 and 13) may be polymerized by adding asuitable polymerization catalyst, which is normally one of the freeradical type but may also be, for example, an anionic or cationiccatalyst, or by irradiating with a high-energy source such as anelectron beam or a beam of radioactively produced particles (e.g., fromradioactive cobalt) into the polymer. This latter method is described indetail as to its general applicability in US. Pat. 3,247,012, thedisclosure of which is incorporated by reference herein.

The chemical nature of the resinous compositions of this invention isnot known with certainty, and is not considered critcal. It is believedthat the compositions prior to curing consist mainly of simple mixturesof component A and component B, said mixtures being capable of formingsolutions or dispersions when fused. Component B is believed to beprimarily involved in the po lymerization.

Because of the simplicity of polymerization methods involving them, thecompositions of this invention which already contain polymerizationcatalysts are particularly suitable for use in the home. For example,the solid composition of Example 4 may be applied to an inexpensivesubstrate such as plywood, chipboard and the like and covered with apiece of release paper. Upon the application of heat-for example, withan ordinary household iron-polymerization takes place and a decorativecoating is applied on the surface. Similarly, the compositions can beused as adhesives for fastening thin, flexible films to surfaces of thistype.

In some instances when a plurality of resinous materials is used in acomposition of this invention, a coating may be formed which is rich inone resin on the surface and rich in the other in the interior. Forexample, a composition of this invention may be prepared from diacetoneacrylamide, an unsaturated polyester and an acrylic resin. During thecuring reaction after a film has been formed, the diacetone acrylamidecrosslinks the polyester which strikes in to the surface of the objectbeing coated, while the surface film remains rich in the acrylic resinwhich is more resistant to weathering and therefore particularlysuitable for outdoor use.

What is claimed is:

1. A composition which is solid at room temperature, said compositioncomprising (A) a polymer containing not more than about one ethylenicunit for each 20 polymeric units and (B) a compound of the formulawherein each of R R and R is hydrogen, a lower alkyl radical, or ahydroxyalkyl or alkoxyalkyl radical, each of R and R is hydrogen or alower alkyl radical, and R is hydrogen, halogen or a lower alkylradical; said composition forming, upon liquefaction, a solution ordispersion of component A in component B.

2. A composition according to claim 1 wherein component B is diacetoneacrylamide.

3. A composition according to claim 2 wherein component A is athermoplastic polymer.

4. A composition according to claim 3 which consists essentially ofabout 2-70 parts by weight of component A, about 98-30 parts(respectively) of diacetone acrylamide, and about 0-2.5 parts each of anantioxidant and a polymerization catalyst.

5. A resinous composition formed by polymerizing the composition ofclaim 4.

6. A resinous composition according to claim 8 wherein component B isdiacetone acrylamide.

7. A resinous composition according to claim 6 wherein component A is athermoplastic polymer.

8. A resinous composition formed by subjecting the composition of claim1 to free radical polymerization conditions, thereby causingpolymerization of component B.

References Cited UNITED STATES PATENTS 3,277,056 10/ 1966 Coleman 260-633,425,942 2/ 1969 Coleman 25251.5 3,518,326 6/1970 Forsberg 260828 OTHERREFERENCES Higgins et al., A Versatile New Component For ImprovedCoatings, Journal of Pain: Technology, Vol. 41, No. 530, pp. -196, March1969.

MURRAY TILLMAN, Primary Examiner J. ZIEGLER, Assistant Examiner US. Cl.X.R.

204159.l5, 159.16, 159.17; 26086l N, 836, 837 R, PV, 844, 873, 875, 878R, 884, 885, 886

